Phenolic amido resin



Patented Dec. 8, 1942 rnENouc AMIDO ansm Herman A. Bruson, Philadelphia, Pa assignor to The Besinous Products 8; Chemical Philadelphia, Pa.

No Drawing.

17 Claims.

This invention relates to new resinous materials and to the process by which they are prepared. It relates more particularly to a novel type of resinous reaction product obtained by heating the anhydride of a polycarboxylic acid with a tertiary aminomethyl phenol or a carboxylic acid salt or ester thereof.

Tertiary aminomethyl phenols may be obtained by condensing a phenol having a reactive hydrogen atom in ortho or para position with respect to the hydroxyl group, with a suitable aldehyde, such as formaldehyde and a secondary non-aromatic amine as is described in United States Patents Nos. 2,031,557, 2,033,092, 2,040,039, 2,040,040, and 2,098,869.

It has been found that, when these tertiary aminomethyl phenols, their carboxylic acid salts or esters are heated with the anhydride of a poly- Company,

Application January 4, 1940, Serial No. 312,338 g carboxylic acid containing at least four carbon atoms, resinous products are obtained. The reaction is carried out at temperatures above about 100 C. but below the decomposition temperature of reactants or products, preferably between 120 and 200 C. The tertiary aminomethyl phenol (or its salt or ester) and the anhydride of the acid may be heated alone or they may be dissolved in an inert solvent having a sufiiciently high boiling point such as xylene or tetralin. The properties of the resins thus obtained may be varied over a wide range depending on the particular acid anhydride and tertiary aminomethyl phenol employed.

A great many so-called methylol-forming phenols may be condensed with an aldehyde and a secondary non-aromatic amine in preparing the starting materials for the present invention. These include phenol, ocor fi-naphthol, cresols, phenyl phenols, cyclohexyl phenols, p-ter.butyl phenol, hydroxy diphenyl methanes, hydroxy diphenyl sulfones. hydroxy benzophenone, etc. Secondary non-aromatic amines which may be employed include dimethylamine, methylethylamine, diethylamine, dibutylamine, diallylamine, dimethallylamine, methyloctylamine, methyldodecylamine, and other dialkyl amines, diethanolamine, N-methylcyclohexylamine, dicyclohexylamine, piperidine, morpholine, pyrrolidine, etc. One mol of the phenol may be condensed with one mol each of the secondary amine and aldehyde to yield compounds containing one tertiary aminomethyl group or, than one reactive nuclear hydrogen atom, two or more mols of the secondary amine and aldehyde may be employed to yield compounds having the corresponding number of tertiary aminomethyl groups. Non-aromatic secondary diamines such if the phenol has more as piperazine and N,N dimethyl-decamethylenediamine-LIO may also be employed in which case either one or two mols of the phenol and aldehyde may be condensed with one mol of the diamine.

Formaldehyde, or other suitable aldehyde such as glyoxal, or benzaldehyde, may be used in 'preparing the tertiary aminomethyl phenols.

Typical tertiary aminomethyl phenols which may be used are:

- dihy' droxydi- 2,5-di(dimethylaminomethyl) -hydroquinone 2,4,6 tri- (dimethylaminomethyl) -phenol 3,5,3',5' -,tetra(dimethylamincmethyl)- 4,4'- dihydroxydiphenyl-p-propane.

The aromatic nucleus of the phenolic amines used may contain substituents other than those radicals.

The anhydrides of polycarboxylic acids which may be used to react with the tertiary aminomethyl phenols include compounds from the allphatic, aromatic, hydroaromatic, and heterocyclic series, particularly good results being obtained with phthalic, hexahydrophthalic, succinic, glutaric, adipic, azelaic, sebacic, and py'romellitic anhydrides. Darker resins are obtained with .maleic, citraconic and furoic anhydrides. Furthermore, there may be used as the acid anmaleic anhydride with other unsaturated compounds, such as abietic acid. abietic acid esters,

styrene, indene, vinyl acetate, vinyl ethers,

acrylic acid esters, methacrylic acid esters, terpenes, drying oils, drying oil fatty acids, castor oil, etc., which adducts possess at least one polycarboxylic acid anhydride group. It is not always necessary to employ the anhydride of the acid as the acids themselves may be used provided that they are readily dehydrated to the anhydride by heating to the temperatures employed in the process described here. Furthermore, two or more acid anhydrides may be employed with one tertiary aminomethyl phenol or a mixture of tertiary aminomethyl phenols may be employed with one or more acid anhydrides. When the tertiary aminomethyl phenol contains more than one tertiary aminomethyl group, one of them may be neutralized with a monobasic or polybasic carboxylic acid prior to reacting with the polybasic acid anhydride. Likewise, when mixtures of two tertiary aminomethylphenols are employed, the amino group oi. one of them may be neutralized with a monocarboxvlic or polycarg5 boxylic acid. Suitable acids for this purpose are stearic, palmitic, oleic, hydroxystearic. acrylic, crotonic, methacrylic, sorbinic, undecylenlc, lactic, elaeostearic, linolic. linoleic, octadecadi'enic, naphthenic, abietic, lauric, montanic, benzoyl benzoic, phenoxyacetic acids, or polybasic 'acids such'as adipic, azelaic, sebacic. or phthalic acids. The resinous character of the final products may also be modified by heating them with monobasic acids such as abietic, linseed oil fatty acids, etc.

The reaction between the tertiary aminomethyl phenol and the anhydride of the dibasic acid is generally carried out by mixing the reactants in the proportion of one mol of the anhydride for each'aminomethyl group in the tertiary amlno methyl phenol and heating to temperatures between 120 and 200 C. until the reaction is complate. The resulting product is usually a pale amber-colored resin.

When the tertiary aminomethyl phenol contains nuclear alkyl substituents, the final products tend to become soluble in hydrocarbons, whereas when these substituents are absent, the final products are soluble in alcohol. Those tertiary aminomethyl phenols'which contain more than one tertiary aminomethyl group yield harder resins when reacted with the polycarboxylic acid anhydride than do the phenolic amines which contain only one such group. If the aryl nucleus carries more than one phenolic hydroxyl group, the products may be rendered insoluble by prolonged heating.

When the proportion of reactants indicated above is employed, the product contains free phenolic hydroxy groups which may be esterifled by heating with monoor poly-carboxylic acids or' their anhydrides. In the case of the polycarboxylic acid, this esteriflcaton may be brought about by using an excess 01' the acid anhydride in the original reaction mixture. In cases. dialkanolamine, such as diethanolamine, is em ployed in making the tertiary aminomethylpheno], the alcoholic hydroxyl groups of the resulting product may also, be esterifled by heating with monoor poly-carboxylic acids or anhydrides.- Alternatively, the tertiary aminomethyl phenol may be esterifled at the phenolic hydroxy group prior to reacting it with the polycarboxylic acid anhydride as described in copending application Serial No. 240,009 iiled November 12, 1938, now Patent No. 2,218,739. The products obtained from the esterifled aminomethtyl phenols are somewhat softer and more 5 readily soluble in hydrocarbons than those obtained from the unesterified ones.

When the products contain replaceable hydroen atoms in the ortho or para position with respect to the phenolic hydroxyl group, they may or alkaline solution toyield resins which are much harder than the initial product.

The term phenolic radical is here used to describe aromatic groups possessing free nuclear hydroxyl groups or phenolic ester groups which are capable of being hydrolyzed to hydroxyl groups. The phenolic radical may possess one or more benzene rings. In the latter case they may be Joined directly togethe as in naphthol, go phenyl phenol, hydroxyphenanthrene, hydroxyanthracene, etc., or through a bridge of sulfur, oxygen or carbon, as in p,p'-dihydroxydiphenylsulfoxide, -sulilde, or -sulione, 4,4'-dihydroxydiphenyl ether, or p,p'-dihydroxydiphenyl methane, etc. a

The following examples are illustrative of the general process which has been described. The

parts shown are by weight.

Example 1 Example 2 A' mixture of 444 anhydride and 248 parts (1 mol) of 2,4,6-tri- (dimethylaminomethyl)-phenol is heated and stirred in an atmosphere of nitrogen for three and one-half hours at 130-135" C. The resin obtained is a pale reddish, hard, brittle mass which is soluble in alcohol and can be heated for many hours without increasing in viscosity.

' The tri- (dimethylaminomethyl) -phenol used is a colorless oil, B. P. 130-135 C./l mm., obtainable by condensing one mol of phenol with three mols each of formaldehyde and dimethylamine.

' Example 3 sodium hydroxide solution, or inammonia, The

alcoholic solution may be used as a varnish. The 5-tertiary-butyl-2-hydroxybenzyl N dimethyla mine is a colorless oil, B. P. 100-110" C./12'mm.,

dimethyiamine, formaldehyde, and p-ter.butylphenol at 90 C. for three hours. If dibutylamine or a higher clialkylamine is used in place of the di-methylamine in preparing the tertiary aminomethyl phenol, the final resin obtained by heating.

be condensed with formaldehyde in acid, neutral, 1

parts (3 mols) 01 phthalic obtainable by heating one mol equivalent each of this aminomethyl phenol with phth'alic anhydride as carbons and'drying oils.

. Example 4 Example 5 A mixture 0! 148 parts of phthalic anhydride and 193 parts of o-hydroxybenzyl-N-morpholine is heated at 130-135 C. for three hours with stirring. The product is a hard, brittle, ambercolored resin which is soluble in alcohol.

Example 6 A mixture oi 148 parts of phthalic anhydride and 2'77 parts of 1-(-dimethylaminobenzyl)-2- naphthol is heated at ISO-160 C. for three hours with stirring in an atmosphere of carbon dioxide. The product is a hard, brittle, amber-colored resin.

Example 7 A mixture of 100 parts of succinic anhydride and 317 parts of 1-(a-piperidino-benzyD-2- naphthol yields a brittle, amber-colored resin when heated for three hours at 140-150" C.

Example 8 A mixture of 113 parts of o-hydroxybem 11-N- dimethylamine and 300 parts 0! maleic anhydride-abietic acid adduct (crystalline) isheated mr three hours at 135 C. The product is a hard, brittle resin soluble in alcohol.

Example 9 A mixture consisting of 29.6 g. of phthalic anhydride and 22.8 g. of 3,5,3',5'-tetra-(dimethylaminomethyl) -4,4'-dihydroxydiphenyl-p-propane on (onomcnrocmmonm (a crystalline compound melting at 82-83 0., obtainable by condensing four mols each of formaldehyde and dimethylamine with one mol of p,p'-dihydroxydiphenyl-p-propane) is heated at 130-140 C. with stirring. A clear, pale yellow, hard, brittle resin is obtained after about 15 minutes heating. On further heating,.the resin becomes insoluble in dilute acids, alkalies, and organic solvents.

described above is soluble in petroleum hydro- 'p,p-dihydroxydiphenyl-p-propane exa ple 10 A mixture 0114.8 8.1)! phthalic anhydride and 28.5 "BT01 S-(dimethylaminomethyl) 4,4-dihydroxydiphenyl-p-propane CHQN(CH3)1 (obtainable by condensing one molecular equivalent each of formaldehyde, dimethylamine and at 90 C.) is heated during 15 minutes to 150' C. and held there for two hours. A hard, pale amber-colored resin is obtained. It melts at 85-90 C. and ,is soluble in alcohol. It may be used as a shellac substitute. On heating for an additional 30 minutes at 185 C. this resin becomes insoluble in ordinary organic solvents. It is a pale amber- I colored, hard, transparent, vitreous mass which becomes rubbery when hot. By using 28.5 g. o! sebacic anhydride in place of phthalic anhydride and heating as above, a very tough, hard'resln may be obtained. This resin is insoluble in the ordinary organic solvents.

Example 11 The maleic anhydride adduct of methyl abietate was prepared by heating 31.6 g. of methyl abietate with 9.8 g. of maleic anhydride at 175 C. for one hour. 28.5 g. of 3-(dimethylamino methyl) 4,4- dihydroxydiphenyl 13 propane is constantly.

added to the crude adduct thus obtained and the mixture heated at -150 C. for three hours in an atmosphere of carbon dioxide while being stirred. The product is a pale amber-colored, hard, brittle resin. It is soluble in a 1:1 mixture of alcohol and benzene or in glycol monoethyl ether.

Example 12 A mixture consisting of 30.7 parts or 3-(dimethylaminomethyl) -4,4'-dihydroxydiphenylsulfone ommcm):

HO-O-sm-OMX and 14.8 parts of phthalic anhydride is heated at -155 C. for one and one-half hours in an atmosphere of carbon dioxide while being stirred The product is an extremely pale, hard resin. An alcoholic solution of this resin deposits a hard, glossy film on evaporation of the solvent.

The sulione used in this example may be prepared as follows: i

A mixture of 250 g. of 4,-i-dihydroxydiphenylsulfone and g. of aqueous 25% dimethylamine solution was cooled while 100 g. of aqueous 30% formaldehyde solution was added. This mixture was stirred and heated under a reflux condenser Iorthree hours at 90-95 C. The oily layer was then separated while hot and washed thoroughly with hot water. After drying under reduced pressure at 80-90 C. the'product was obtained as a hard solid consisting essentially of 3- (dimethylaminomethyl) -4,4'-dihydroxy phenylsulfone.

' Example 13 A mixture consisting of 25.5, parts of 3-(dimethylaminomethyl) -4-hydroxybenzophenone amen).

and 15.4 parts 01' hexahydrophthalic anhydride is heated at 150-155 C. for two hours while stirring constantly. The product is a pale reddish, hard, brittle resin.

Example 14 Example 15 A mixture of 49.8 part of o-dimethylamino methyl-p-ter. butylphenyl acetate CH:N(CH2):

CH -CH;

H: and 29.6 parts of phthalic anhydride is heated in an atmosphere of carbon dioxide at 145-153 C. for two hours and forty minutes. A pale amber,

brittle resin, soluble in alcohol and in toluol, is v obtained.

Example 16 A mixture consisting 01' 14.8 g. of phthaiic anhydride and 31.1 g. of 2- (dimethylaminomethyl) 4-ter.butylphenyl benzoate is heated for 4-5 hours at l-155 C. in an atmosphere oi carbon dioxide while being stirred. A pale amber-colored, tough resin is obtained.

Example 17 14.8 g. of phthalic anhydride is heated at 150 C. with 23.4 g. or the sebacic acid ester of 2- (dimethylaminomethyl) -phenol having the formula ooccnmcoo l I (oatmeal-O Ocmmonm After two hours heating, asoft, tough, paleamber colored resin is obtained.

Example 18 A mixture consisting of 14.8 g. of phthalic anhydride and 62.6 g. of the monostearic acid salt of di- (dimethylaminomethyl) 4,4'-dihydroxydiphenyldimethyl methane was heated for one hour at 150-160 C, A hard, alcohol-soluble, resinousmass was obtained which, upon further heating, became rubbery and insoluble in organic solvents.

Example 19 A mixture of 28.4 g. of stearic acid, 14.8 g. of phthalic anhydride, 20.7 g. of 2- (dimethylaminomethyl)-4-ter.butylphenol, and 28.5 g. of 3- (dimethylaminomethyl) -4,4'-dihydroxydiphenyldimethyl methane was heated for 2 hours at 140- 145 C. An amber-colored, hard, resinous wax was obtained which wassoluble in alcohol.

The products obtained from the reaction between the tertiary aminomethyl phenol and the 7 anhydride or a polycarboxylic acid are resinous substances which resemble shellac in many re.- spects. 'They may be used in the preparation oi spirit varnishes, inks, and enamels. Theyare in many cases thermoplastic and, hence, can'be used for molding, laminating, and as adhesives. The hardness, solubility, and fusibility' can be varied considerably by varying theconditions of reaction, the nature and proportions oi the tertiary aminomethyl phenol and the polycarboxylic acid anhydride. I

I claim: I

1. The process for preparing a resin which comprises heating above C. and below decomposition temperatures the anhydride of a polybasic carboxylic acid containing at least our carbon atoms with a tertiary aminomethyl phenol.

2. The process for preparing a resin which comprises heating between about and about 200 C. the anhydride 01' a polybasic carboxylic acid containing at least four carbon atoms with a tertiary aminomethyl phenol.

3. Process for prises heating above 100 C. and below decomposition temperatures an anhydride of a polybasic carboxylic acid containing at least four carbon atoms and at least one member or the group consisting of tertiary aminomethyl phenols, their carboxylic acid salts and esters.

4. Process for preparing a resin which oomprises heating above 100 C. and below decomposition temperatures an anhydride of a polybasic carboxylic acid containing at least four carbon atoms and a mixture or at least two tertiary aminomethyl phenols.

5. Process for preparinga resin which comprises heating above 100 C. and below decomposition temperatures an anhydride of a polybasic carboxylic acid containing at least four carbon atoms and a mixture consisting of a tertiary aminomethyl phenol and a carboxylic acid salt of a tertiary aminomethyl phenol.

6. The process for preparing aresin which comprises heating between about 120 and about 200 C. phthalic anhydride with a tertiary aminomethyl phenol.

7. A process for preparing a resin which comprises heating between about 120 C. and about 200 C. phthalic anhydride and 3- (dimethylaminom'ethyl) -4,4'-dihydroxydiphenyl-p-propane.

8. A process for preparing a resin which comprises heating between about 120 and about "200 C. phthalic anhydride and 5-ter.butyl-2-hydroxybenzyl-N-dibutylamine.

9. Process for preparing a resin which comprises heating between about 120 and about 200 C. phthalic anhydride, 2-(dimethylaminometh yl) -4-tertiary butyl phenol, 3-(dimethylaminomethyl) -4,4' dihydroxydiphenyldimethyl methane, and stearic acid. I

10. The resinous product obtained by heating above 100 C. and below decomposition temperatures the anhydride of a polycarboxylic acid containing at least four carbon atoms and tertiary aminomethyl phenol.

11. The resinous product obtained by heating between about 120 and about 200C. the anhy-- I dride of a polybasic carboxylic acid containing at least four carbon atoms with a tertiary aminomethyl phenol.

12. The resinous product obtained by heating above 100 C. and below decomposition tempera-'- V tures an anhydride of a 'polybasic carboxylic acid containing at least four carbon atoms and at least one member of the group consisting of preparing a resin which com- 10 stearic acid.

phthalic anhydride and 3-(dimethyiaminomethyl) 4,4-dihydroxydiphenyl-p-propane.

16. The resinous product obtained by heating phthalic anhydride and 5-ter.buty1-2-hydroxybenzyl-N-dibutylamine.

17. The resinous product obtained by heating phthalic anhydride, 2-(dimethy1aminomethyD-4- tertiary butyl phenol, 3- (dimethylaminomethyl) 4,4-dihydroxydiphenyidimethy1 methane, and

HERMAN A. BRUSON. 

